CN114725459B - Proton exchange membrane and preparation method thereof - Google Patents
Proton exchange membrane and preparation method thereof Download PDFInfo
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- CN114725459B CN114725459B CN202210452276.8A CN202210452276A CN114725459B CN 114725459 B CN114725459 B CN 114725459B CN 202210452276 A CN202210452276 A CN 202210452276A CN 114725459 B CN114725459 B CN 114725459B
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- isocyanate
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- exchange resin
- unsaturated ester
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- 239000012528 membrane Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 81
- 229920005989 resin Polymers 0.000 claims abstract description 81
- 239000012948 isocyanate Substances 0.000 claims abstract description 77
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 65
- 150000002148 esters Chemical class 0.000 claims abstract description 45
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 40
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000005286 illumination Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 238000000016 photochemical curing Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000013067 intermediate product Substances 0.000 claims description 19
- 230000009257 reactivity Effects 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003729 cation exchange resin Substances 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000013007 heat curing Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000007086 side reaction Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 3
- 206010016807 Fluid retention Diseases 0.000 description 3
- 238000003848 UV Light-Curing Methods 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- DSSXKBBEJCDMBT-UHFFFAOYSA-M lead(2+);octanoate Chemical compound [Pb+2].CCCCCCCC([O-])=O DSSXKBBEJCDMBT-UHFFFAOYSA-M 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- 229920002556 Polyethylene Glycol 300 Polymers 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a proton exchange membrane and a preparation method thereof, wherein the preparation raw materials of the proton exchange membrane comprise: proton exchange resins, isocyanates, unsaturated esters, and photoinitiators; wherein, the proton exchange resin contains hydroxyl; the unsaturated ester contains hydroxyl; the isocyanate contains at least two isocyanate groups; and (3) carrying out photocuring film formation on the reaction product of the proton exchange resin, isocyanate and unsaturated ester to obtain the proton exchange membrane. According to the invention, unsaturated ester is grafted on the proton exchange resin through isocyanate, so that a photo-curable group (unsaturated double bond) is introduced into the proton exchange resin, and a photoinitiator is introduced into the preparation raw material of the proton exchange membrane, under the existence of a photo-curable energy source and the photoinitiator, the proton exchange membrane can be formed by adopting illumination, the high temperature is not required in the illumination film forming process of the proton exchange membrane, the problem of large energy consumption caused by the traditional heat curing process can be solved, and the requirements of green and environment protection are met.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a proton exchange membrane and a preparation method thereof.
Background
The proton exchange membrane battery fuel cell is a device capable of converting chemical energy into electric energy, and has the advantages of green, high conversion efficiency, high power density, low noise and reproducibility. The proton exchange membrane is a core element of the proton exchange membrane fuel cell, and can be used for conducting protons in the proton exchange membrane fuel cell and blocking fuel and oxidant, and is also a support of a catalyst in the proton exchange membrane fuel cell.
Proton exchange membranes are generally prepared by forming a film of proton exchange resin, and are generally formed by a heat curing method, and the temperature required in the heat curing process is high, so that the problem of high energy consumption is caused.
Disclosure of Invention
Based on the problems, the invention provides a proton exchange membrane with low energy consumption and a preparation method thereof, which aim to solve the problems of large energy consumption caused by preparing the proton exchange membrane in a heat curing film forming mode in the prior art.
A proton exchange membrane, the proton exchange membrane comprising:
proton exchange resins;
an isocyanate;
unsaturated esters; and
a photoinitiator;
wherein, the proton exchange resin contains hydroxyl; the unsaturated ester contains hydroxyl; the isocyanate contains at least two isocyanate groups, and the reactivity of different isocyanate groups is different;
and (3) carrying out photocuring film formation on the reaction product of the proton exchange resin, isocyanate and unsaturated ester to obtain the proton exchange membrane.
Preferably, the proton exchange resin includes at least one of a strong acid cation exchange resin containing sulfonic acid groups and a weak acid cation exchange resin containing carboxylic acid groups.
Preferably, the isocyanate comprises at least one of 2, 4-toluene isocyanate, 2, 6-toluene isocyanate or isophorone diisocyanate and diphenylmethane diisocyanate.
Preferably, the proton exchange membrane is prepared from a raw material further comprising a solvent.
Preferably, the unsaturated ester comprises at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, 2-acrylic acid (4-hydroxybutyl) ester.
The invention also provides a preparation method of the proton exchange membrane, which comprises the following steps:
adding unsaturated ester into the isocyanate, adjusting the reaction temperature to enable isocyanate groups with high reactivity in the isocyanate to react with the unsaturated ester, and obtaining an intermediate product after the reaction is finished;
adding the proton exchange resin into the intermediate product, and increasing the reaction temperature to enable isocyanate groups with low reactivity in the intermediate product to react with the proton exchange resin, and obtaining the oligomer resin after the reaction is finished;
and adding a photoinitiator into the oligomer resin, and placing the oligomer resin under the illumination condition to form a film, thus obtaining the proton exchange membrane.
Preferably, the isocyanate is prepared through modification treatment, so that the prepared proton exchange membrane has better water retention;
the step of the modification treatment comprises the following steps:
and (3) reacting the isocyanate with polyethylene glycol under the condition of pH 5-6 to obtain the modified isocyanate.
Preferably, the solid content in the proton exchange resin is 60% -80%.
Preferably, the molar ratio of hydroxyl groups in the unsaturated ester to isocyanate groups in the isocyanate is (2 to 2.05): 1.
Preferably, the mass concentration of the photoinitiator is 0.05% -5%.
Compared with the prior art, the invention has the following beneficial effects:
according to the proton exchange membrane, grafting modification is carried out on a common proton exchange resin, and based on the reaction of isocyanate groups (-NCO) and hydroxyl groups (-OH), unsaturated ester is grafted on the proton exchange resin through isocyanate, so that a photo-curable group (unsaturated double bond) is introduced into the proton exchange resin, and a photoinitiator is introduced into a raw material for preparing the proton exchange membrane, and the proton exchange membrane can be formed by adopting illumination conditions and the cooperation of the photoinitiator, so that the high temperature is not required in the illumination film forming process of the proton exchange membrane, the problem of energy consumption in a large amount caused by the traditional heat curing process can be solved, and the preparation cost of the proton exchange membrane is reduced.
The reactivity of the isocyanate groups in the isocyanate can be different, and the reaction temperature can be set according to the reactivity of the isocyanate groups, so that the reaction sequence of different isocyanate groups in the isocyanate can be controlled, and side reaction products are generated in the water reduction reaction process.
The isocyanate group (-NCO) in the isocyanate has the advantages of difficult occurrence of gel phenomenon and less side reaction, and the unsaturated ester is grafted on the proton exchange resin through the isocyanate, so that the conversion rate of the proton exchange membrane is improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The experimental methods in the following examples are conventional methods unless otherwise specified. The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified. The quantitative tests in the following examples were all set up with three replicates, and the data are the mean or mean ± standard deviation of the three replicates.
In addition, "and/or" throughout this document includes three schemes, taking a and/or B as an example, including a technical scheme, a technical scheme B, and a technical scheme that both a and B satisfy; in addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The invention provides a proton exchange membrane, which is prepared from raw materials including proton exchange resin, isocyanate, unsaturated ester, photoinitiator and solvent, wherein the proton exchange resin contains hydroxyl; the unsaturated ester contains hydroxyl; the isocyanate contains at least two isocyanate groups, and the reactivity of different isocyanate groups is different; and (3) carrying out photocuring film formation on the reaction product of the proton exchange resin, isocyanate and unsaturated ester to obtain the proton exchange membrane.
According to the proton exchange membrane, grafting modification is carried out on a common proton exchange resin, and based on the reaction of isocyanate groups (-NCO) and hydroxyl groups (-OH), unsaturated ester is grafted on the proton exchange resin through isocyanate, so that a photo-curable group (unsaturated double bond) is introduced into the proton exchange resin, and a photoinitiator is introduced into a raw material for preparing the proton exchange membrane, and the proton exchange membrane can be formed by adopting illumination conditions and the cooperation of the photoinitiator, so that the high temperature is not required in the illumination film forming process of the proton exchange membrane, the problem of energy consumption in a large amount caused by the traditional heat curing process can be solved, and the preparation cost of the proton exchange membrane is reduced.
The reactivity of the isocyanate groups in the isocyanate can be different, and the reaction temperature can be set according to the reactivity of the isocyanate groups, so that the reaction sequence of different isocyanate groups in the isocyanate can be controlled, and side reaction products are generated in the water reduction reaction process.
The isocyanate group (-NCO) in the isocyanate has the advantages of difficult occurrence of gel phenomenon and less side reaction, and the unsaturated ester is grafted on the proton exchange resin through the isocyanate, so that the conversion rate of the proton exchange membrane is improved.
In some embodiments, the photoinitiator is 0.1% to 0.5% by mass of the unsaturated ester.
In some embodiments, the proton exchange resin comprises at least one of a strong acid cation exchange resin comprising sulfonic acid groups and a weak acid cation exchange resin comprising carboxylic acid groups.
Specifically, both the sulfonic acid group and the carboxylic acid group in the proton exchange resin can be used for proton transfer, and have hydrophilicity.
In some embodiments, the isocyanate comprises at least one of 2, 4-toluene isocyanate, 2, 6-toluene isocyanate, or isophorone diisocyanate, and diphenylmethane diisocyanate.
In some embodiments, the proton exchange membrane preparation feedstock further comprises a catalyst.
In some embodiments, the catalyst comprises at least one of stannous octoate, dibutyltin dilaurate, lead octoate, zinc naphthenate, and tetraisobutyl titanate.
In some embodiments, the proton exchange membrane preparation feedstock further includes a solvent for diluting the concentration of the proton exchange resin.
Further, the photo-curing film forming speed is high, and the efficiency of preparing the proton exchange membrane is improved, so that the volatilization of the solvent in the film forming process is reduced, and the requirements of green environmental protection are met.
In some embodiments, the solvent comprises at least one of N, N-dimethylformamide, dimethyl sulfoxide, acetone, and ethylene glycol dimethyl ether.
In some embodiments, the mass of the solvent is 0-20% of the total mass of the proton exchange membrane preparation feedstock.
Specifically, the solvent is used to dilute the proton exchange resin to reduce the concentration of the proton exchange resin. The invention has low solvent consumption and can reduce the pollution of the solvent to the environment.
In some embodiments, the unsaturated esters include at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, 2-acrylic acid (4-hydroxybutyl) ester.
The invention also provides a preparation method of the proton exchange membrane, which comprises the following steps:
s100, adding unsaturated ester into isocyanate, and adjusting the reaction temperature to enable isocyanate groups with high reactivity in the isocyanate to react with the unsaturated ester, and obtaining an intermediate product after the reaction is finished.
The invention selects unsaturated ester containing hydroxyl, the hydroxyl in the unsaturated ester reacts with one isocyanate group in isocyanate, specifically, when the isocyanate is selected as 2, 4-toluene isocyanate and the unsaturated ester is selected as hydroxyethyl acrylate, the reaction equation is as follows:
wherein,is 2, 4-toluene isocyanate; />Is hydroxyethyl acrylate;is an intermediate product.
Further, a first catalyst may be added in step 100 to increase the reaction rate of the isocyanate and unsaturated ester. In some embodiments, the first catalyst is at least one of triethylamine, triethylenediamine, stannous octoate, dibutyltin dilaurate, lead octoate, cobalt octoate, iron octoate, zinc naphthenate, and tetraisobutyl titanate.
Specifically, the reaction temperature of step 100 is 20-40 ℃, preferably 25 ℃; the reaction time is preferably 2h.
In some embodiments, solvent dilution can be added to the proton exchange resin, and the solvent is used for diluting the proton exchange resin to reduce the concentration of the proton exchange resin.
In some embodiments, the solids content of the proton exchange resin solution is 60% to 80%.
In some embodiments, the isocyanate may be modified to provide a proton exchange membrane with better water retention.
Preferably, the step of modifying treatment comprises:
and (3) reacting the isocyanate with polyethylene glycol under the condition of pH 5-6 to obtain the modified isocyanate.
The molar ratio of isocyanate to polyethylene glycol is preferably 2:1 to reduce the occurrence of side reactions.
Specifically, hydroxyl groups (-OH) at both ends of polyethylene glycol are respectively reacted with one isocyanate group of different isocyanates.
In some embodiments, the polyethylene glycol (PEG) is preferably at least one of PEG100, PEG200, PEG300, and PEG 400.
In some embodiments, an acid may be added to the reaction solution of isocyanate and polyethylene glycol to adjust the pH to 5-6.
In some embodiments, when the modified proton exchange membrane is used in step S100, a polymerization inhibitor should be used to prevent the reaction of unsaturated esters with modified isocyanates from polymerization.
Preferably, the polymerization inhibitor is selected from hydroquinone.
S200, adding the proton exchange resin solution into the intermediate product, and increasing the reaction temperature to enable isocyanate groups with low reactivity in the intermediate product to react with the proton exchange resin, and obtaining the oligomer resin after the reaction is finished.
Specifically, the reaction equation of the intermediate product prepared in the step S100 and the proton exchange resin is as follows, wherein the isocyanate in the step S100 is selected as 2, 4-toluene isocyanate, and the unsaturated ester is selected as hydroxyethyl acrylate for listing:
wherein,is proton exchange resin solution, +.>An oligomer resin.
Specifically, R 1 、R 2 The main structure of the proton exchange resin can be selected according to the mechanical strength of the proton exchange membrane, for example, the proton exchange membrane with higher mechanical strength can select R with more benzene ring structures 1 、R 2 。
The isocyanate groups in the intermediate product prepared in the step S100 react with the hydroxyl groups in the proton exchange resin.
Further, a second catalyst may be added in step S200 to accelerate the reaction rate of the proton exchange resin with the intermediate product. In some embodiments, the second catalyst is at least one of triethylamine, triethylenediamine, stannous octoate, dibutyltin dilaurate, lead octoate, cobalt octoate, iron octoate, zinc naphthenate, and tetraisobutyl titanate.
In some embodiments, the total mass of the first catalyst and the second catalyst is from 0.2% to 1% of the total mass of the proton exchange membrane manufacturing feedstock, the first catalyst and the second catalyst being collectively referred to as the catalyst.
Specifically, the reaction temperature in step S200 is 60-75deg.C, preferably 75deg.C; the reaction time is preferably 2h.
As can be seen from steps S100 and S200, in the present invention, the reactivity of the isocyanate groups in the isocyanate is different, and the reaction temperature can be set according to the reactivity of the isocyanate groups, so as to control the reaction sequence of the different isocyanate groups in the isocyanate, further control that the intermediate product contains only one isocyanate group, the hydroxyl group in the unsaturated ester reacts with one isocyanate group in the isocyanate, and one hydroxyl group in the proton exchange resin reacts with another isocyanate group in the isocyanate, so that the molar ratio of the hydroxyl group in the proton exchange resin, the isocyanate group in the isocyanate and the hydroxyl group in the unsaturated ester is preferably 1:2:1, so as to reduce the occurrence of side reaction and reduce the phenomenon of incomplete reaction, thereby improving the yield of the proton exchange membrane. If the molar ratio of hydroxyl groups in the proton exchange resin, isocyanate groups in the isocyanate and hydroxyl groups in the unsaturated ester is preferably not 1:2:1, but is selected to be 1:2:1.5, the hydroxyl groups in the unsaturated ester that are added in step S100 will react with another isocyanate group in the isocyanate, resulting in only a portion of the hydroxyl groups in the proton exchange resin in step S200 reacting with another isocyanate group in the isocyanate, resulting in a portion of the proton exchange resin unreacted and resulting in side reactions of the isocyanate that all react with the unsaturated ester.
S300, adding a photoinitiator into the oligomer resin, and forming a film under the ultraviolet light condition to obtain the proton exchange tree film.
Further, under the condition of illumination, the photoinitiator absorbs energy of illumination wavelength to generate free radicals and cations, so that the oligomeric resin containing double bonds is crosslinked and cured, and a proton exchange membrane is formed.
Specifically, the present invention is not limited to the photoinitiator and the wavelength range of the light waves corresponding to the photoinitiator.
In some embodiments, the unsaturated ester contains hydroxyl groups in a molar ratio of hydroxyl groups in the unsaturated ester to isocyanate groups in the isocyanate of (2-2.05): 1.
In some embodiments, the mass concentration of the photoinitiator is between 0.05% and 5%.
Example 1
Adding N, N-dimethylformamide into strong acid cation exchange resin containing sulfonic group to dilute into proton exchange resin solution with solid content of 60-80%.
At normal temperature, slowly adding hydroxyethyl acrylate into 2, 4-toluene isocyanate within 15 minutes, heating to 60 ℃, and reacting for 60-120 minutes while keeping the temperature, thus obtaining an intermediate product.
Adding intermediate product and 0.1% stannous octoate into the proton exchange resin solution, mixing and stirring for half an hour, heating to 75 ℃, preserving heat and reacting for 2 hours to obtain the oligomer resin with the solid content of 50-60%.
Adding 0.05% of photoinitiator 1173 (2-hydroxy-2-methyl-1-phenyl-1-acetone) into the synthetic oligomer resin, forming a film on a coating machine, and forming a film under the illumination condition (the UV curing wavelength of an LED lamp is between 350 and 400nm, and the distance between the UV lamp and the surface of the oligomer resin is 7 to 15 cm) to obtain the proton exchange membrane.
Wherein the molar ratio of the proton exchange resin to the 2, 4-toluene isocyanate to the hydroxyethyl acrylate is 1:1:1.
Example 2
Adding N, N-dimethylformamide into strong acid cation exchange resin containing sulfonic group to dilute into proton exchange resin solution with solid content of 60-80%.
And (3) regulating the pH value to 5-6 by adding phosphoric acid into the PEG200, slowly adding the PEG200 with the pH value of 5-6 into 2, 4-toluene isocyanate within 15 minutes at normal temperature, heating to 60 ℃, and preserving heat for 30-70 minutes to obtain the modified double-blocked isocyanate.
Slowly adding hydroxyethyl acrylate and 0.01% of hydroquinone polymerization inhibitor into the modified double-blocked isocyanate, heating to 60 ℃, reacting for 30min while keeping the temperature, adding dilaurate, heating to 75 ℃, keeping the temperature for 2h, and reacting to obtain an intermediate product.
Adding the intermediate product and 0.01% stannous octoate into the proton exchange resin solution, mixing and stirring for half an hour, heating to 75 ℃, preserving heat and reacting for 2 hours to obtain the oligomer resin with the solid content of 40-50%.
Adding 0.05-5% of photoinitiator 1173 (2-hydroxy-2-methyl-1-phenyl-1-acetone) into the synthetic oligomer resin, forming a film on a coating machine, and forming a film under the illumination condition (the UV curing wavelength of an LED lamp is 350-400nm, and the distance between the UV lamp and the surface of the oligomer resin is 7-15 cm) to obtain the proton exchange membrane.
Wherein, the molar ratio of PEG200 to 2, 4-toluene isocyanate is 1:2.
The molar ratio of the proton exchange resin to the modified double-blocked isocyanate to the hydroxyethyl acrylate is 1:1:1.
Example 3
Adding solvent N, N-dimethylformamide into strong acid cation exchange resin containing sulfonic group to dilute into proton exchange resin solution with solid content of 60-80%.
Slowly adding hydroxyethyl acrylate into isophorone diisocyanate at 60 ℃ within 15 minutes, and keeping the temperature for reaction for 60-120 minutes to obtain an intermediate product.
Adding the intermediate product and 0.1% of dilaurate into the proton exchange resin solution, mixing and stirring for half an hour, heating to 75 ℃, preserving heat and reacting for 2 hours to obtain the oligomer resin with the solid content of 60-70%.
Adding 0.05-5% of photoinitiator 1173 (2-hydroxy-2-methyl-1-phenyl-1-acetone) into the synthetic oligomer resin, forming a film on a coating machine, and forming a film under illumination conditions (the UV curing wavelength of an LED lamp is 350-400nm, and the distance between the UV lamp and the surface of the oligomer resin is 7-15 cm) to obtain the proton exchange membrane.
Wherein the molar ratio of the proton exchange resin to the isophorone diisocyanate to the hydroxyethyl acrylate is 1:1:1.
Example 4
Adding acetone into weak acid cation proton exchange resin containing carboxylic acid groups to dilute into proton exchange resin solution with solid content of 60-80%.
At normal temperature, slowly adding hydroxyethyl acrylate into 2, 4-toluene isocyanate within 15 minutes, heating to 60 ℃, and reacting for 60-120 minutes while keeping the temperature, thus obtaining an intermediate product.
Adding intermediate product and 0.1% stannous octoate into the proton exchange resin solution, mixing and stirring for half an hour, heating to 75 ℃, preserving heat and reacting for 2 hours to obtain the oligomer resin with the solid content of 50-60%.
Adding 0.05% of photoinitiator 1173 (2-hydroxy-2-methyl-1-phenyl-1-acetone) into the synthetic oligomer resin, forming a film on a coating machine, and forming a film under the illumination condition (the UV curing wavelength of an LED lamp is between 350 and 400nm, and the distance between the UV lamp and the surface of the oligomer resin is 7 to 15 cm) to obtain the proton exchange membrane.
Wherein the molar ratio of the proton exchange resin to the 2, 4-toluene isocyanate to the hydroxyethyl acrylate is 1:1:1.
Performance testing
The proton exchange membranes prepared in examples 1, 2, 3 and 3 were tested for thickness, swelling ratio, water absorption, strength, load, and proton conductivity, and the experimental results are shown in the table.
Table 1 experimental results
As is clear from Table 1, the water absorption of example 2 was significantly higher than that of examples 1, 3 and 4 after the modification of the double blocked isocyanate in example 2, and it was confirmed that the water retention of the proton exchange membrane obtained after the modification of the double blocked isocyanate was enhanced.
The swelling rate of the proton exchange membranes prepared by the invention is less than 10%, which indicates that the proton exchange membranes prepared by the embodiments 1-4 have good dimensional stability.
As shown in the table, the proton exchange membrane prepared by the invention has proton conductivities of respectively more than 75ms/cm, 16ms/cm and 2ms/cm when the relative humidity is 80%, 50% and 20%, which proves that the proton exchange membrane prepared by the invention has better proton conductivities.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (8)
1. The proton exchange membrane is characterized by comprising the following preparation raw materials:
proton exchange resins;
an isocyanate;
unsaturated esters; and
a photoinitiator;
wherein the proton exchange resin contains hydroxyl; the unsaturated ester contains hydroxyl; the isocyanate contains at least two isocyanate groups, the reactivity of the different isocyanate groups is different, and the isocyanate comprises at least one of 2, 4-toluene isocyanate, 2, 6-toluene isocyanate or isophorone diisocyanate and diphenylmethane diisocyanate;
photo-curing the reaction product of the proton exchange resin, the isocyanate and the unsaturated ester to form a film, thus obtaining the proton exchange membrane;
the molar ratio of hydroxyl groups in the proton exchange resin, isocyanate groups in the isocyanate and hydroxyl groups in the unsaturated ester is 1:2:1.
2. The proton exchange membrane according to claim 1, wherein the proton exchange resin comprises at least one of a strong acid cation exchange resin containing sulfonic acid groups and a weak acid cation exchange resin containing carboxylic acid groups.
3. The proton exchange membrane according to claim 1, wherein the proton exchange membrane is prepared from a feedstock further comprising a solvent.
4. The proton exchange membrane of claim 1, wherein the unsaturated ester comprises at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, 2-acrylic acid (4-hydroxybutyl) ester.
5. A method of preparing a proton exchange membrane according to any one of claims 1 to 4, comprising the steps of:
adding unsaturated ester into the isocyanate, adjusting the reaction temperature to enable isocyanate groups with high reactivity in the isocyanate to react with the unsaturated ester, and obtaining an intermediate product after the reaction is finished;
adding the proton exchange resin into the intermediate product, and increasing the reaction temperature to enable isocyanate groups with low reactivity in the intermediate product to react with the proton exchange resin, and obtaining the oligomer resin after the reaction is finished;
and adding a photoinitiator into the oligomer resin, and placing the oligomer resin under the illumination condition to form a film, thus obtaining the proton exchange membrane.
6. The method for preparing a proton exchange membrane according to claim 5, wherein the isocyanate is prepared by modifying, and the modifying step comprises:
and under the condition of pH of 5-6, reacting the isocyanate with polyethylene glycol, and respectively reacting hydroxyl (-OH) at two ends of the polyethylene glycol with one isocyanate group in different isocyanates to obtain the modified isocyanate.
7. The method for producing a proton exchange membrane according to claim 5, wherein the solid content in the proton exchange resin is 60% to 80%.
8. The method for preparing a proton exchange membrane according to claim 5, wherein the mass concentration of the photoinitiator is 0.05% -5%.
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